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Steam has more energy than boiling water does (40.7 kJ vs 5 kJ). So when the steam hits your skin you are immediately feeling 40.5 KJ of heat rather than 5KJ. Steam also absorbs heat so it will also increase in temperature.
If you look at a phase change graph, you will see that the change between liquid and gas is represented by a straight line in which heat is increasing but the substance has not yet changed phases. Therefore, steam holds a greater temperature.
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